New azo dyestuffs



United States Patcnt NEW AZO DYESTUFFS Hans R. Bolliger, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application December 27, 1954, Serial No. 477,933

Claims priority, application Switzerland December 28, 1953 6 Claims. (Cl. 260-162) This invention provides valuable new azo-dyestutis, which contain an acid group imparting solubility in water but contain no N-acylated sulfonic acid amide groups, and also contain a group of the formula in which R represents an alkylene radical which may contain substituents, Z represents the radical of an organic sulfonic acid bound through an oxygen atom of its functional group to R, and n represents a whole number not greater than 2.

The radical Z in the groups of the Formula 1 is advantageously present in the 'y-position, or preferably in the B-position, of the alkylene radical R which is bound to the -SO2 group in OL-POSltiOD either through the NH group when (n=2) or directly (when 11:1). Especially valuable are the dystulfs of this invention which contain a group of the Formula 1, in which Z represents the radical of an aliphatic or aromatic sulfonic acid.

In .addition to agroup of the Formula 1, the dyestuffs of this invention contain an acid group imparting solubility in water such, for example, as a -SO2NH2 group, a sulfone group, for example a methylsulfone group, a

caiboxyl group, or advantageously a sulfonic acid group,

but no N-acylated sulfonic acid amide group.

The acid group imparting solubility and the group of the Formula 1 may be present in the dyestutf molecule in any desired positions, that is to say, a group of eachkind may be present in the radical of a single component or one dyestuif component may contain, for example, the group imparting solubility, and the other component may contain the group of the Formula 1. Especially valuable are those monoazo-dyestuifs of the latter kind, which contain the group of the Formula 1 in the radical of the diazo component and the acid group imparting solubility in the radical of the coupling component.

In making the dyestuffs of the invention there are advantageously used dyestutf components which alreadycontain the aforesaid groups. The dyestuff components to be used may, of course, contain other substituents such, for example, as halogen atoms, nitro groups, acylamino groups, alkyl groups or alkoxy groups. However, there are advantageously used diazo compounds which contain no hydroxyl group in ortho-position to the diazo group.

As examples of starting materials there may be men tioned the following:

A. Components which contain .a group of the Formula 1, such as diazo compounds of the following amines: 1- aminobenzene-4-sulfonic acid-fi- (ethane sulfonyloxy)- ethylamide, 1-aminobenzene-3- or -4-sulfonic acid-,B-(benzene sulfonyloxy)-ethylamide, 1-aminobenzene-4-sulfonic acid-'y-(benzene sulfonyloxy)-propylamide, l-aminoben zene-4-sulfonic acid-p-(para-toluene sulfonyloxy)-propylamide, 1-aminobenzene-3- or -4-sulfonic acid-B-(parw toluene sulfonyloxy)-ethylamide, l-aminobenzene-B-sultonic acid-N-methyl-N:,B- (para toluene sulfonyloxy)- 2,799,672 Patented July 16, 1951 ice ethylamide, -4-methy1-l-aminobenzene-3-sulfonic acid-fl- (para-toluene su1fon-yloxy)-ethylamide, 2:5-dichloro-1- aminoben-zene-4-sulfonic acid B-(benzene 'sulfonyloxy)- ethylamide, 2-methoxyl-l-aniinobenzene-S-B-(para-toluene sulfonyloxy)-ethyl sulfone, 1-aminobenzene-2-, -3- or -4- sulfonic acid-,B-(para-toluene sulfonyloxy)-ethyl sulfone and 4-methyl-1-aminobenzene-3-sulfonic acid-,B-(benzene sulfonylox-y) -ethylamide, and the following coupling components: Z-aminonaphthalene-6 sulfonic acid-,B-(benzene sulfonyloxyyethylamide, 1-hydroxynaphthalene-4- or -5-tsulfonic :acid-fi-(benzene sulfony1oxy)-ethylamide, 2- hydroxynaphthalene 6 sulfonic .acid-fi-(benzene .sulfonyloxy)-eth ylamide, 2-hydroxynaphthalene-6--(benzene sulfonyloxy) -ethy1 sulfone, 1-phenyl 3-methyl-S-pyrazolone- 2'-, -3"- or -4-sulfonic acid-p-(benzene sulfonyloxy) -ethy1- amide, 1-phenyl-3-methyl-5-pyrazolone-3'-sulfonic acid- 'yi( benzene su'lfonylox-y) -propylam'i'de, l-phenyl-3 -methyl- 5-pyrazolone-3'sfl-(para toluene .sulfonyloxy)-ethyl sulfone and ,1 pheny1-3-methyl-5-pyrazolone-3-sulfonic acidfl-(para-toluene sulfonyloxy)-ethylamide.

. B. Components containing an acid group imparting solubility of the kind mentioned above, such as diazo compounds of 1-arninobenzene-3- or -4-sulfonic acid amide, 1-aminobenzene-2, -3- or -4-methyl sulfone, l-aminobenzene-2 -3- or -4-sulfonic acid, Z-methylor 2-methoxy-1- aminobenzene-4- or -5sulfonic-acid, Z-aminonaphthalene- 6-sulfonic acid, .and the following coupling components: 1-.hydroxynaphthalene-4- or -5-sulfonic acid, 2-hydroxynaphthalene-3-, -4:, -'5-, -'6-, -'7- or 8- sulfonic acid, 2:9- dihydroxynaphtha1ene-6-sulfonic acid, Z-aminonaphthalene-6-sulfonic acid, Z-amino-8-hydroxynaphthalene-6- sulfonic acid, l-phenyl-5-pyrazolone-3-carboxylic acid, 1- phenyl-3-methyl-5-pyrazolone-2'-, -3- or -4-sulfonic acid, -1-- (-2 -chlorophenyl)-3-methyl-5 -pyrazolone 4' --sulfonic acid and 1-(2:5'-dichlorophenyl)3-methyl-5-pyrazolone- 4-sulfonic acid.

The monoazo-dyestufls obtainable from the foregoing components by coupling a diazo compound mentioned under B with a coupling component mentioned under A or above all by coupling a diazo compound under A with a coupling component under B in a not strongly alkaline, and advantageously neutral to acid, medium, are new.

They are azo-dyestufis which contain at least one acid group imparting solubility, but no N-acylated sulfonic acid amide group, and a group of the above Formula 1.

Especially valuable are the monoazo-dyestufis of the formula :(2) RTN=N-PZ SOz-(NH),.-1(CHz)m-OSO -Z in which R represents the radical of a diazo-component of the naphthalene or advantageously benzene series, Z represents .an aliphatic or aromatic radical, m represents them/hole number 2 or 3, 11 represents a whole number not greater than 2, and Pz represents a 5-pyrazo1one radical which contains in the 3- or advantageously 1- position an aryl radical containing a sulfonic acid group as a substituent.

The dyestufis can be used for dyeing or printing a very wide variety vof materials especially nitrogenous natural or artificial 'fibers such as leather, silk, wool and structures of superpolyamides or superpolyurethanes. They are suitable for dyeing from a weakly acid to approximately neutral bath. The dyeings -.so obtained are uniform and are distinguished by their good fastness to light and their excellent fastness to washing, fulling and alkali.

The following examples illustrate the invention, the partsand percentages being by weight:

Example 1 35.5 parts of 4-aminobenzene-p-(paratoluene-wlfonYloxy)-ethyl sulfone are diazotized in 100 parts of water and 25 parts of hydrochloric acid (density=1.18) with 6.9 parts of sodium nitrite, and the diazo compound is coupled witha solution of 26 parts of l-phenyl-S-methyl- 5-pyrazolone-4'-sulfonic acid and 30 parts of crystalline sodium acetate in 250 parts of water. When the coupling is finished the resulting dyestuif of the formula fochloride in pyridine followed by acid splitting of the acetylarnino group) are diazotized as described in Example l, and coupled with a solution of 26 parts of 1- phenyl-3-methyl-5 pyrazolone 3'-sulfonic acid and 30 parts of crystalline sodium acetate in 250 parts of water. By working up in the usual manner there is obtained the dyestufi which in form of its sodium salt corresponds to N-O-SOIINB.

Example 2 40 parts of l-methoxy-Z-aminobenzene-4-sulfonic acid- N- 8-(para toluene sulfonyloxy) ethylamide (prepared from 1-methoXy-2-acetylaminobenzene 4 sulfonic acid- N-p-hydroxyethylamide by reaction with paratoluene sul- OH is salted out with sodium chloride, filtered and dried. 15 1116 formula The new dyestufi, an orange-red powder, dissolves in water a red-yellow coloration and dyes wool from a Weakly acid bath pure yellow tints of excellent fastness to washing, fulling and light.

From the diazo components and coupling components mentioned in columns I and II of the following table there are obtained by the above method similar dyestuffs which dye wool from neutral to weakly acid baths in the tints given in column 111:

1 11 III Diazo component Coupling component I or V C=N\ 1 NHFOS oIN HCH:CHz0S OPO I /NSO3H greenish yellow.

CH=O I CH: OCHa I 01 I C= l 2 NHa /N SO3H Do.

on=o I 01 OH so,NH-oH,-oH,-os0=--om CH3 CH3 I 3 somu-om-cm-o-sm-Q I /N@ pure yellow.

on=o I SOaH 0H OH: OH

4 TSOr-NH-CHr-CHr-O-SO2- CHI; I yellow red.

NH: SO|H cm on 6 SOeNHCHz-GH;OS0=-OCH: HO red.

SOzH

f: i 11 m. Diazoeomponent Coupling component (EH OH 6 -r BOrN'Ef6H1CHlO -SO:OOH| HAN (acid coupling) reddish bordeaux. -S0:H

N'Hiocn' I lean v 7.. NH; /N yellow.

. I "CBC,

. H I -so,-NH-cn,crr,0 sorH Gas-432 I 8 H1N- I yellow orange.

NH, Son-NH I HnCHrO ib,

O C H:

=N 9 NH N yellow.

S O 2-NH fls-O-SOrCrHt The 2-aminonaphthalene--sulfonic acid ,8-(tosyloxy)-ethylamide necessary for making dyestufi No. 8 of the above table can be prepared, for example, by treating Z-acetylamino naphthalene-6-sulfonic acid-fi-hydroxyethylamide in pyridine with para-toluene sulfochloride, pouring the reaction mixture into ice water, and hydrolyzing the acetyl group in the resulting reaction product with dilute hydrochloric acid with the aid of heat.

Example 3 0.5 part of the dyestufi obtainable as described in Example 1 is dissolved in 4000 parts of water, 10 parts Of crystalline sodium sulfate are added, and 100 parts of well wetted wool are entered into the resulting dyebath at -50" C. 2 parts of acetic acid of 40 percent strength are then added, the temperature is raised to the boil in the course of /2 hour, and dyeing is carried on at the boil for hour. Finally the wool is rinsed with cold water and dried. There is obtained a level yellow dyeing of good fastness to light and excellent fastness to washing.

A level yellow dyeing of good fastness to light and excellent fastness to washing is also obtained by proceeding in the manner described above, but without the addition of acetic acid to the dyebath.

What is claimed is:

1. A monoazo dyestufi which in its free acid form corresponds to the formula Hahn-O-SOr-R:

wherein R, R1 and R2 each represents a benzene radical, and m represents a whole number up to 2.

2. A monoazo dyestufi which in its free acid form corresponds to the formula wherein m, n and p each represents a whole number up to two, X and Y each represents a member selected from the group consisting of a chlorine and a hydrogen atom.

3. The monoazo dyestuif which in its free acid form corresponds to the formula 4. The monoazo dyestuff which in-- its free-aeid-form 6. The monoazo dyestufi whichin its free and form corresponds to the formula corresponds to the formula 01 H H0 t, 0H: 77 I v OCH; GN

G-N som 5 N=N0 N=NO 803B 1 o C=N V C=N v I (BE; CH:

SO2NH SO2-NH (l: GHrCHrOSO2CH2CHa Hr-CHz-O-SO CHI References Cited in the file of this patent 5. The monoazo dyestufi which in its free acid form UNITED STATES PATENTS corresponds to the formula 1,857,244 Hentnch et a1. May-10, 1932 2,424,493 Muller et a1. July 22, 1947 C-N N=N-C I H I SOs-NH 

1. A MONOAZA DYESTUFF WHICH IN ITS FREE ACID FORM CORRESPONDS TO THE FORMULA 